JPH0625228B2 - Method for producing silicon-containing vinyl polymer - Google Patents
Method for producing silicon-containing vinyl polymerInfo
- Publication number
- JPH0625228B2 JPH0625228B2 JP61237108A JP23710886A JPH0625228B2 JP H0625228 B2 JPH0625228 B2 JP H0625228B2 JP 61237108 A JP61237108 A JP 61237108A JP 23710886 A JP23710886 A JP 23710886A JP H0625228 B2 JPH0625228 B2 JP H0625228B2
- Authority
- JP
- Japan
- Prior art keywords
- containing vinyl
- silicon
- vinyl polymer
- monomer
- styrene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/087—Binders for toner particles
- G03G9/08702—Binders for toner particles comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- G03G9/08706—Polymers of alkenyl-aromatic compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/087—Binders for toner particles
- G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
- G03G9/08791—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775 characterised by the presence of specified groups or side chains
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/087—Binders for toner particles
- G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
- G03G9/08793—Crosslinked polymers
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Developing Agents For Electrophotography (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、スチレンとケイ素含有ビニル単量体より構成
される新規な共重合体の製造方法に関する。TECHNICAL FIELD The present invention relates to a method for producing a novel copolymer composed of styrene and a silicon-containing vinyl monomer.
（発明が解決しようとする問題点） 従来、電子写真現像剤の現像性を向上させるために、電
子写真現像剤に種々の物質を添加することが試みられて
おり、より優れた現像性を示す帯電制御剤を見出だす努
力がなされている。(Problems to be Solved by the Invention) Conventionally, in order to improve the developability of an electrophotographic developer, it has been attempted to add various substances to the electrophotographic developer, and it shows better developability. Efforts are being made to find a charge control agent.
したがって、本発明の目的は、電子写真現像剤の帯電制
御剤として使用可能な新規なケイ素含有ビニル重合体の
製造方法を提供することにある。Therefore, an object of the present invention is to provide a method for producing a novel silicon-containing vinyl polymer that can be used as a charge control agent for an electrophotographic developer.
（問題点を解決するための手段） 本発明者等は、ケイ素含有樹脂について鋭意検討した結
果、ある特定のケイ素含有ビニル単量体を用いて製造し
た重合体が、電子写真現像剤の帯電制御剤として使用し
た場合に、帯電性が向上することを発見し、本発明を完
成するに至った。(Means for Solving the Problems) The inventors of the present invention have conducted diligent studies on silicon-containing resins, and as a result, found that a polymer produced by using a specific silicon-containing vinyl monomer is capable of controlling the charge of an electrophotographic developer. It was discovered that when used as an agent, the chargeability was improved, and the present invention was completed.
本発明のケイ素含有ビニル重合体の製造方法は、スチレ
ン単量体９９．９〜８０モル％と、下記一般式(I) （式中、Ｒは低級アルキル基を示し、ｋは０又は１〜３
の整数を示す。） で示される単量体０．１〜２０モル％とを、水性媒体中
で共重合させることよりなることを特徴とするものであ
る。本発明の製造方法によって得られるケイ素含有ビニ
ル重合体は、ガラス転移点９０〜１００℃を有する３次
元構造の重合体であって、スチレン単位と下記一般式(I
I) （式中、Ｒは低級アルキル基を示し、ｋは０又は１〜３
の整数を示す。） で表される単量体とが９９．９：０．１乃至８０：２０
のモル比で不規則に配列した構造を有している。The method for producing a silicon-containing vinyl polymer of the present invention comprises a styrene monomer of 99.9 to 80 mol% and the following general formula (I): (In the formula, R represents a lower alkyl group, and k is 0 or 1 to 3
Indicates an integer. And 0.1 to 20 mol% of the monomer represented by the formula (4) are copolymerized in an aqueous medium. The silicon-containing vinyl polymer obtained by the production method of the present invention is a polymer having a three-dimensional structure having a glass transition point of 90 to 100 ° C. and has a styrene unit and the following general formula (I
I) (In the formula, R represents a lower alkyl group, and k is 0 or 1 to 3
Indicates an integer. ) The monomer represented by 99.9: 0.1 to 80:20
It has a structure in which it is irregularly arranged at a molar ratio of.
本発明を更に詳細に説明すると、本発明の上記ケイ素含
有ビニル重合体は、スチレンと前記一般式(I)で表され
る単量体とを９９．９：０．１乃至８０：２０のモル比
で共重合させることにより製造される。スチレンと前記
一般式(I)で表されるケイ素含有ビニル単量体との反応
は、水性媒質中で乳化重合させることによって行われ
る。この際乳化重合は、乳化剤を使用しないで行うのが
好ましい。共重合は、単量体と水との比１０：９０〜４
５：５５（容量比）の下で、公知の重合開始剤を用い
て、例えば、水溶液濃度１０−５〜５×１０−２ｍｏｌ
／となるように添加し、重合温度４５〜８０℃に於い
て、５〜４５時間反応させることによって行なうことが
できる。重合終了後、反応液から共重合体を遠心分離
し、凍結乾燥して固形化する。The present invention will be described in more detail. The silicon-containing vinyl polymer of the present invention comprises styrene and a monomer represented by the general formula (I) in a molar ratio of 99.9: 0.1 to 80:20. It is produced by copolymerizing in a ratio. The reaction between styrene and the silicon-containing vinyl monomer represented by the general formula (I) is carried out by emulsion polymerization in an aqueous medium. At this time, emulsion polymerization is preferably performed without using an emulsifier. The copolymerization is carried out at a ratio of monomer to water of 10: 90-4.
Under 5:55 (volume ratio), using a known polymerization initiator, for example, an aqueous solution concentration of 10 −5 to 5 × 10 −2 mol
It can be carried out by adding it so that it becomes / and reacting for 5 to 45 hours at a polymerization temperature of 45 to 80 ° C. After completion of the polymerization, the copolymer is centrifuged from the reaction solution and freeze-dried to solidify.
本発明において、前記一般式(I)で示されるケイ素含有
ビニル単量体とのスチレンに対する重合比率が、モル比
で０．１より低いと、得られる重合体を電子写真現像剤
の帯電制御剤として使用した場合の効果が充分でなくな
り、また、２０％よりも高い場合には、上記単量体のゲ
ル化が進行するために、重合安定性が低下する。In the present invention, the polymerization ratio of styrene with the silicon-containing vinyl monomer represented by the general formula (I) is less than 0.1 in terms of molar ratio, the resulting polymer is a charge control agent for electrophotographic developer. When it is used as the above, the effect is not sufficient, and when it is higher than 20%, gelation of the above-mentioned monomer proceeds, so that the polymerization stability is lowered.
本発明の方法により得られるケイ素含有ビニル重合体
は、ガラス転移点９０〜１００℃の３次元構造の共重合
体であって、スチレン単位と前記一般式(II)で表される
単量体単位とが不規則に結合した２次元構造を有する。
即ち、スチレンと一般式(I)で表される単量体とが共重
合によって線状に不規則に配列し、そして上記一般式
(I)で表される単量体中のケイ素原子が互いにシロキサ
ン結合によって架橋した構造を有している。The silicon-containing vinyl polymer obtained by the method of the present invention is a copolymer having a three-dimensional structure having a glass transition point of 90 to 100 ° C., and a styrene unit and a monomer unit represented by the general formula (II). It has a two-dimensional structure in which and are irregularly connected.
That is, styrene and the monomer represented by the general formula (I) are linearly and irregularly arranged by copolymerization, and the above general formula
It has a structure in which the silicon atoms in the monomer represented by (I) are crosslinked with each other by a siloxane bond.
したがって、本発明のケイ素含有ビニル重合体は溶剤、
例えば、トルエン、アセトン、テトラヒドロフラン、ジ
クロロメタン、メチルエチルケトンなどに対する溶解度
が０．１％以下である。Therefore, the silicon-containing vinyl polymer of the present invention is a solvent,
For example, the solubility in toluene, acetone, tetrahydrofuran, dichloromethane, methyl ethyl ketone, etc. is 0.1% or less.
（実施例） 以下、本発明を実施例によって説明する なお、以下の実施例中、ガラス転移点（Ｔｇ）は、測定
器として、島津ＤＴ−４０（島津製作所製）を用い、ア
ルミニウムセル中に、重合体微粉末を入れ（リファレン
スは空セル）、１０℃／分の割合いで昇温し、吸熱の立
上り点をＴｇとして測定した。(Examples) Hereinafter, the present invention will be described by way of examples. In the following examples, the glass transition point (Tg) was measured using a Shimadzu DT-40 (manufactured by Shimadzu Corporation) as a measuring instrument in an aluminum cell. The polymer fine powder was added (reference was an empty cell), the temperature was raised at a rate of 10 ° C./min, and the rising point of endotherm was measured as Tg.
また、赤外吸収スペクトルは、日立製作所（株）製）を
用い、重合体の微粉末をＫＢｒと共に圧縮成型して測定
した。In addition, the infrared absorption spectrum was measured by using Hitachi, Ltd.) and compression molding fine polymer powder together with KBr.
傾斜パドル型攪拌翼、窒素導入口、温度調節計及び単量
体滴下ロートを備えた１０のガラスリアクターに、水
５６００mlを仕込み、窒素ガスで置換した後、６０℃に
昇温した。攪拌翼の回転数は２５０ｒｐｍに調節した。
次いで、滴下ロート中に、単量体として、スチレン６３
０ｇ及び下記構造式で示されるケイ素含有ビニル単量体
７０ｇ（東レシリコーン（株）製、ＳＺ−６０３２）の
混合液を仕込み、リアクターにセットした。Water (5600 ml) was charged into 10 glass reactors equipped with an inclined paddle type stirring blade, a nitrogen inlet, a temperature controller and a monomer dropping funnel, and the temperature was raised to 60 ° C. after replacement with nitrogen gas. The rotation speed of the stirring blade was adjusted to 250 rpm.
Then, as a monomer, styrene 63 was added to the dropping funnel.
A mixed liquid of 0 g and 70 g of a silicon-containing vinyl monomer represented by the following structural formula (SZ-6032 manufactured by Toray Silicone Co., Ltd.) was charged and set in a reactor.
温度が恒温になったことを確認した後、重合開始剤とし
てＶ−５０（和光純薬（株）製）５．７ｇを含む水溶液
１００mlを添加し、引き続いて、上記単量体の混合液の
滴下した。重合は、単量体の混合液の滴下を開始した時
点から２４時間継続した。 After confirming that the temperature became constant, 100 ml of an aqueous solution containing 5.7 g of V-50 (manufactured by Wako Pure Chemical Industries, Ltd.) as a polymerization initiator was added, and subsequently, a mixed solution of the above monomers was added. Dropped. The polymerization was continued for 24 hours from the time when the dropping of the mixed liquid of the monomers was started.
重合反応の終了後、エマルジョンの一部を遠心分離し、
乾燥して同定を行なった。このものの分折結果は次の通
りであった。After the completion of the polymerization reaction, centrifuge part of the emulsion,
It was dried for identification. The results of this analysis were as follows.
ガラス転移点：１００℃ 元素分折値 Ｈ：７．７３％ Ｃ：９０．８２％ Ｎ：０．３９％ 粒径：０．２μｍ（走査型電子顕微鏡） 粒度分布：ほぼ単分散 得られた共重合体は、テトラヒドロフラン、トルエン、
ジクロロメタン、メチルエチルケトンに不溶であった。
このもののＥＳＣＡスペクトルによってＳｉ元素が確認
された。また、その赤外吸収スペクトルは図面に示す通
りであった。Glass transition point: 100 ° C. Elemental breakdown value H: 7.73% C: 90.82% N: 0.39% Particle size: 0.2 μm (scanning electron microscope) Particle size distribution: Almost monodisperse The polymer is tetrahydrofuran, toluene,
It was insoluble in dichloromethane and methyl ethyl ketone.
The ESCA spectrum of this product confirmed the Si element. The infrared absorption spectrum was as shown in the drawing.
（発明の効果） 本発明の方法により得られるケイ素含有ビニル重合体
は、電子写真現像剤の帯電制御剤として有用な物質であ
り、それを用いると、電子写真現像剤の摩擦帯電性及び
流動性が向上する。(Effect of the Invention) The silicon-containing vinyl polymer obtained by the method of the present invention is a substance useful as a charge control agent for an electrophotographic developer, and when it is used, the triboelectric chargeability and fluidity of the electrophotographic developer are improved. Is improved.
図面は、本発明の方法により得られる。ケイ素含有ビニ
ル重合体の赤外吸収スペクトルのグラフである。The drawings are obtained by the method of the invention. It is a graph of an infrared absorption spectrum of a silicon-containing vinyl polymer.
Claims (1)
下記一般式(I) （式中、Ｒは低級アルキル基を示し、ｋは０又は１〜３
の整数を示す。） で示される単量体０．１〜２０モル％とを、水性媒体中
で共重合させることよりなることを特徴とするガラス転
移点９０〜１００℃を有する３次元構造の重合体であっ
て、スチレン単位と下記一般式(II) （式中、Ｒは低級アルキル基を示し、ｎは０又は１〜３
の整数を示す。） で表される単量体単位とが不規則に配列した構造を有す
るケイ素含有ビニル重合体の製造方法。1. A styrene monomer of 99.9 to 80 mol%,
The following general formula (I) (In the formula, R represents a lower alkyl group, and k is 0 or 1 to 3
Indicates an integer. ) A polymer having a three-dimensional structure having a glass transition point of 90 to 100 ° C., characterized by comprising copolymerizing 0.1 to 20 mol% of the monomer represented by , A styrene unit and the following general formula (II) (In the formula, R represents a lower alkyl group, and n is 0 or 1 to 3
Indicates an integer. ) A method for producing a silicon-containing vinyl polymer having a structure in which the monomer unit represented by
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61237108A JPH0625228B2 (en) | 1986-10-07 | 1986-10-07 | Method for producing silicon-containing vinyl polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61237108A JPH0625228B2 (en) | 1986-10-07 | 1986-10-07 | Method for producing silicon-containing vinyl polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6392622A JPS6392622A (en) | 1988-04-23 |
| JPH0625228B2 true JPH0625228B2 (en) | 1994-04-06 |
Family
ID=17010530
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61237108A Expired - Fee Related JPH0625228B2 (en) | 1986-10-07 | 1986-10-07 | Method for producing silicon-containing vinyl polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0625228B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW243455B (en) * | 1993-02-09 | 1995-03-21 | Ciba Geigy |
-
1986
- 1986-10-07 JP JP61237108A patent/JPH0625228B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6392622A (en) | 1988-04-23 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |